The structural evolution of B₂Si_n^–/0 (n = 3–12) clusters were investigated by anion photoelectron spectroscopy and ab initio calculations. The two B atoms in B₂Si_3–12^–/0 incline to form a B–B bond and more B–Si bonds. The lowest-lying isomers of B₂Si₃^–/0 have planar structures, while those of B₂Si_4–7^–/0 primarily adopt bowl-shaped based geometries. The two B atoms in B₂Si_8–9^–/0 are not completely encapsulated into the Si_n cages. For B₂Si₁₀^–/0, the two B atoms are completely encapsulated inside the Si₁₀ cage to form a distorted pentagonal prismatic structure. Moreover, B₂Si₁₀^–/0 exhibits 3D aromaticity and B₂Si₁₀ neutral has σ + π double delocalized bonding patterns. B₂Si₁₁^– anion has an endohedral polyhedral cage-like structure, whereas B₂Si₁₁ neutral adopts a bicapped pentagonal prismatic structure with only one interior B atom. The structures of anionic and neutral B₂Si₁₂ are endohedral tetracapped tetragonal prisms. It is interesting that two Si₅ five-membered rings are stabilized by two B atoms in B₂Si₁₀^–/0, while the stabilization of two Si₆ six-membered rings by two B atoms is not observed in B₂Si₁₂^–/0.

中文翻译：

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B ₂ Si _n ^{– / 0}（n = 3–12）团簇的结构演化：尺寸选择的阴离子光电子能谱和理论计算

通过阴离子光电子能谱和从头算计算研究了B ₂ Si _n ^{– / 0}（n = 3–12）团簇的结构演化。B ₂ Si _3–12 ^{– / 0中}的两个B原子倾向于形成一个B–B键和更多的B–Si键。B ₂ Si _3- ^{/ 0}的最低异构体具有平面结构，而B ₂ Si _4-7- ^{/ 0的}异构体主要采用碗形几何形状。B ₂ Si _8–9 ^{– / 0}中的两个B原子没有完全封装到Si _n笼中。对于B ₂ Si_在10 ^{– / 0处}，两个B原子完全封装在Si ₁₀笼内，形成扭曲的五边形棱柱结构。此外，B ₂ Si _10- ^{/ 0}具有3D芳香性，B ₂ Si ₁₀中性具有σ+π双离域键合图案。B ₂ Si ₁₁ ^–阴离子具有内面多面体笼状结构，而B ₂ Si ₁₁中性采用仅具有一个内部B原子的二头状五边形棱柱结构。阴离子和中性B ₂ Si _12的结构是四面体的四面体四面体棱镜。有趣的是，B ₂ Si ₁₀ ^{– / 0}中的两个Si ₅五元环被两个B原子稳定，而B ₂ Si ₁₂ ^–中没有观察到两个B ₆环被两个B原子稳定。^{/ 0}。